查找使用阿拉丁产品的科研文献

Molecular engineering of Co ion–imprinted sites on metal–organic frameworks and facile photodeposition for the selective recovery and upcycling of Co(II)

Xin Liu,Ruixue Hu,Shiran Zhu,Xiangyu Liu,Yu Fang,Yihang Li,Wei Wei

Background The demand for adsorption technologies that facilitate the recovery and upcycling of the valuable metallic element, Co, has been increasing. The recovery of Co from wastewater using metal–organic frameworks (MOFs), which are promising adsorbents, is considerably limited because of the lack of selective adsorption sites. Furthermore, research on the upcycling of Co remains inadequate. Methods Herein, we develop an integrated strategy combining ion imprinting modification and photodeposition for the selective recovery and upcycling of divalent Co ions (Co(II)) using MOF adsorbents. Significant findings First, Co ion–imprinted sites are constructed on a typical MOF adsorbent, MIL-125 (labeled CoIP-ML), via molecular engineering using glycylglycine. Compared with the original aminated MIL-125, CoIP-ML exhibits a superior performance, achieving the maximum adsorption capacity ( q m = 218.6 mg/g) and selectivity (selective coefficient k Co(II)/Ni(II) = 3.61) for Co(II) via the chelation of Schiff base groups and adsorption at terminal carboxyl groups. The Co(II) adsorbed on CoIP-ML is upcycled through a facile photodeposition process into Co oxides, which function as a Fenton-like catalyst. The optimal catalyst effectively activates peroxymonosulfate for the removal of chloroquine diphosphate and chlortetracycline hydrochloride, achieving the upcycling of Co(II). This study presents a unique MOF-functionalization paradigm.

Removals of Cu(II), Ni(II), Co(II) and Ag(I) from wastewater and electricity generation by bimetallic thermally regenerative electro-deposition batteries

Weiguang Wang,Gequn Shu,Hua Tian,Xiuping Zhu

The treatment of heavy metal ions in wastewater is of great significance for protecting the environment and human health. To improve the power density and removal efficiency of thermally regenerative ammonia electro-deposition battery and expand the concentration range of effective wastewater removal, a new method for removing Cu(II), Co(II), Ni(II) and Ag(I) from wastewater while generating high-power electric energy by using waste heat, called bimetallic thermally regenerative electro-deposition battery (B-TREB), was constructed in this work. For Cu(II)-containing wastewater with a wide concentration range of 0.002–0.3 M, the removal efficiency (RE) of Cu/Zn-TREB could reach more than 90%. With the initial concentration of Cu(II) being increased from 0.0005 to 0.3 M, the peak power density was enhanced from 20 to 546 W m −2 . Besides, for 0.01 M and 0.1 M Co(II) wastewaters, the REs of Co/Zn-TREB were 85% and 90%, respectively. The RE of Ni/Zn-TREB was 88% for 0.01 M Ni(II) wastewater. These results illustrated that B-TREBs could remove many kinds of heavy metal ions in the wastewaters while maintaining a high removal efficiency of ~90% over a wide concentration range, and the produced high-power electricity could provide energy for further treatment or other uses.

Spacers-directed structural diversity of Co(II)/Zn(II) complexes based on S-/O-bridged dipyridylamides: electrochemical, fluorescent recognition behavior and photocatalytic properties

Guo-Cheng Liu,Yan Li,Ying Xiong,Xiang-Xiang Liu,Qiao-Min Li,Ju-Wen Zhang,Hong-Yan Lin,Xiao-Wu Li

To investigate the effect of the spacers of S-/O-bridged dipyridylamides on the structures of Co(II)/Zn(II) complexes, [Co(L1)(chda)]·1.5H2O (CP1), [Co(L2)(chda)] (CP2), [Zn(L1)(hip)]·DMA·2H2O (CP3), and [Zn(L2)(hip)]·2.8H2O (CP4) [L1 = N,N′-bis(pyridine-3-yl)thiophene-2,5-dicarboxamide, H2chda = trans-1,4-cyclohexanedicarboxylic acid, L2 = N,N′-bis(pyridine-3-yl)-4,4′-oxybis(benzoic) dicarboxamide, H2hip = 5-hydroxyisophthalic acid, DMA = N,N-dimethylacetamide], have been solvothermally synthesized. X-ray single-crystal diffraction shows that CP1 is a 2-D 3,5-connected network based on Co-L1 linear chains and (Co-chda)2 double chains. CP2 features a 1-D structure derived from 1-D wave-like (Co-chda)2 double chains decorated by terminal L2 ligands. CP3 and CP4 show wave-like (4,4) networks constructed by 1-D Zn-L1 zigzag and Zn-hip zigzag (for CP3)/linear (for CP4) chains. The effect of the spacers of S-/O-bridged dipyridylamides on the structures of the title complexes was discussed. Electrochemical behaviors of CP1–CP2 and solid-state luminescent properties of CP3–CP4 were studied. The luminescence investigations show that CP3 and CP4 are recycled fluorescent probes for environmentally relevant Fe3+ ions. The photocatalytic properties for the degradation of methylene blue (MB) under ultraviolet light irradiation of CP3–CP4 and the recyclable materials after fluorescent sensing Fe3+ ions (named CP3@Fe3+ and CP4@Fe3+) have also been investigated.

Mechanistic Insights into a Co(II)-Coordinated “Free” Metal Site of 2D Zinc-Based MOFs for β-Alkylation of Secondary Alcohols with Primary Alcohols

Weizuo Li,Rui Fu,Jing Shi,Zhenhao Xiao,Yue Xu,Dafang He,Guangyu He,Haiqun Chen,Mingchen Xie

Through in-depth study of the properties and reaction mechanisms of catalysts, it is possible to better optimize catalytic systems and improve reaction efficiency and selectivity. This remains one of the challenges in the field of catalysis. Therefore, the research and design of catalysts play crucial roles in understanding and optimizing catalytic reaction mechanisms. A robust 2D zinc-based MOFs (Zn-HA) supported Co(II) ion catalyst (Zn-HA@Co) has been designed and synthesized via a coordination-assisted strategy for β-alkylation of secondary alcohols with primary alcohols. The characterization demonstrated that the anchoring of Co(II) on Zn-HA via coordination could efficiently enhance the Co(II) ion dispersity and interaction between Co(II) and Zn-HA MOFs. Importantly, the density functional theory results have provided mechanistic insights into the energy of the HOMO and LUMO of the Zn-HA@Co catalyst as well as the energy change of the entire process after interacting with the reactants and the specific energy changes of each orbital. The synthesized Zn-HA@Co MOFs effectively lower the energy barrier of the catalytic reaction process. We expect that our research and design of catalysts will serve as valuable guideline for understanding and optimizing catalytic reaction mechanisms.

Synthesis, structure and anticancer studies of Cu (II), Ni (II) and Co (II) complexes based on 2,3-dihydroxybenzaldehyde-2-(2-aminophenyl)benzimidazole Schiff base

Min Hou,Hou Cong Li,Ning An,Wen Ge Li,Jing Tong

Three metal complexes [Cu(HL)Cl](C 2 H 5 OH) 2 ] (complex 1), [Ni 4 L 2 (CH 3 COO) 4 (C 2 H 5 OH) 4 ] (complex 2) and [CoHL 2 ] (complex 3) based on 2,3-dihydroxybenzaldehyde-2-(2-aminophenyl)benzimidazole Schiff base (H 2 L) were synthesized by solvothermal reaction. The three complexes were characterized by FT-IR spectrometer, elemental analysis, thermogravimetric analysis, and X-ray single-crystal diffraction. X-ray single-crystal diffraction analysis confirmed that complex 1 belongs to monoclinic crystal system with P 2 1 /c space group, and complex 3 crystallizes in trigonal crystal system with R-3 space group. However, complex 2 crystallized in triclinic crystal system with P-1 space group and exhibits centrosymmetric tetranuclear crystallographic structure. Besides, MTT assay was studied antitumor activities against different tumor cells. The results show that the three complexes all have fine anticancer activities. Among them, complex 2 has significantly better anticancer properties against CNE-2Z cells than that of cisplatin. Finally, apoptosis and cell migration were studied to prove that complex 2 could inhibit tumor cells from proliferating in the manner of apoptosis and migration.

Synthesis of a tetrazine-based catecholamide derivative and its evaluation as a chelating agent for removal of Cd(II), Co(II), and Cu(II)

Shan Lei,Bo Jin,Rufang Peng,Qingchun Zhang,Shijin Chu

Three Co(II) complexes with a sexidentate N2O4-donor bis-Schiff base ligand: Synthesis, crystal structures, DFT studies, urease inhibition and molecular docking studies

Hu Wang,Xia Zhang,Yu Zhao,Dongmei Zhang,Fan Jin,Yuhua Fan

Three new N 2 O 4 -donor bis-Schiff base Co(II) complexes, Co(C 36 H 34 N 2 O 8 )·2CH 3 OH ( 1 ), Co(C 28 H 34 N 2 O 8 S 2 )·H 2 O ( 2 ) and Co(C 40 H 36 N 4 O 8 )·3CH 3 OH ( 3 ) with distorted octahedral six-coordinate Co(II) centers were synthesized and determined by single crystal X-ray analysis. The X-ray crystallography shows that the metal atoms of three complexes are all six-coordinate with two nitrogen atoms from C N groups, two oxygen atoms from ether groups and two carboxylic oxygen atoms in the mono-ligand, forming a distorted octahedral geometry. Theoretical studies of the three complexes were carried out by density functional theory (DFT) Becke's three-parameter hybrid (B3LYP) method employing the 6-31G basis set. The DFT studies indicate that the calculation is in accordance with the experimental results. Moreover, inhibition of jack bean urease by Co(II) complexes 1–3 have also been investigated. At the same time, a docking analysis using a DOCK program was conducted to determine the probable binding mode by inserting the complexes into the active site of jack bean urease. The experimental values and docking simulation exhibited that the complex 3 showed strong inhibitory activity (IC 50  = 16.43 ± 2.35 μM) and the structure-activity relationships were further discussed.

Imidazole functionalized organic monoliths for capillary microextraction of Co(II), Ni(II) and Cd(II) from urine prior to on-line ICP-MS detection

Liu Xiaolan,Suo Feiya,He Man,Chen Beibei,Hu Bin

Monoliths composed of poly(1-vinylimidazole-ethylene glycol dimethacrylate), referred to as poly(VI-EGDMA), were modified with imidazole groups and used in capillary microextraction (CME) of trace levels of Co(II), Ni(II) and Cd(II) ions from human urine samples. The effects of sample pH, sample flow rate, sample volume, elution conditions and potentially interfering ions were investigated. Under the optimized conditions, the limits of detection (3σ) are 0.6 ng L −1 for Co(II), 6.4 ng L −1 for Ni(II) and 0.7 ng L −1 for Cd(II), with the relative standard deviations of 1.8 (Co), 4.2 (Ni) and 2.2% (Cd). A Certified Reference Material (ZK018–2, lyophilized human urine) was analyzed to validate the method, and the values found were in good agreement with the certified ones. The method was successfully applied to the analysis of trace Co, Ni and Cd in human urine samples, and the recoveries for spiked samples were in the range from 89% to 105%. The one-step preparation of monolithic material in our perception is an attractive feature for this material which also excels by good extraction performance in that it possesses abundant adsorption sites, good stability and a long lifetime. Two poly(1-vinylimidazole-ethylene glycol dimethacrylate) monolithic capillaries were combined with ICP-MS to improve the analytical speed and used for the analysis of Co(II), Ni(II) and Cd(II) in human urine samples.

Efficient removal of Co(II) from aqueous solution by one-step preparation of heterocyclic ligand-functionalized MOFs: study on adsorption properties and irradiation stability

Peng Yinyin,Pan Ting,Chen Chuang,Zhou Mi,Liu Derong,Feng Jian,Xiong Wei,Liu Ning,Yuan Guoyuan

In this work, MOFs materials functionalized (HC-MOFs) with heterocyclic ligands (thiophene-TPC, pyrrole-PCA and furfural-FUR) were prepared by a one-step method and used for cobalt ion separation studies. The results showed that the maximum adsorption of cobalt ions by the three adsorbents was 141.0 mg/g (UiO-66-TPC), 146.0 mg/g (UiO-66-PCA), and 150.6 mg/g (UiO-66-FUR), respectively, at pH 8.3 and a temperature of 298 K. In addition, The HC-MOFs showed good stability under different doses (0 ~ 200 kGy) of γ-ray irradiation and have great potential for application in the separation of practical radioactive wastewater containing 60 Co.

Ultrafine fragments of a 2D Co(II)-imidazole MOF as cocatalysts for highly efficient and selective visible-light-driven reduction of CO2 to CO

Zhoujie Zhang,Yuhao Li,Jiajia Zhang,Min Fang,Yong Wu

We discovered that triethanolamine (TEOA) can break Co–N bonds in a 2D Co(II)-imidazole MOF, {[Co(TIB) 2 (H 2 O) 4 ]SO 4 } (TIB stands for 1,3,5-tris(1-imidazolyl) benzene) (CoTIB) to form the ultrafine fragments of CoTIB with sizes <5.6 nm under stirring, which are highly efficient and selective (>99%) heterogenous cocatalysts for the visible-light-driven photocatalytic CO 2 reduction reaction to CO. The efficiency of the ultrafine fragments of CoTIB (2.0–4.2 nm) reaches 42.7 mmol g −1  h −1 or a TOF of 33.7 h −1 based on Co atoms, which are among the best of heterogenous cocatalyst for photocatalytic CO 2 RR to CO systems. They are also highly stable under stirring with a TON greater than 909 in 54 h. The ultrafine fragments of CoTIB in mixed solvents were obtained by filtration, using a 0.22-μm filter head, of the 9-h stirred mixture of CoTIB/CH 3 CN/TEOA/trace-H 2 O or the 9-h reaction mixture using 1.0 mg of CoTIB. The fragments of CoTIB in these filtrates were characterized by high-resolution mass spectrometry (HRMS), size distribution and Zeta-potential measurements, ICP-MS, as well as Linear-Sweep-Voltammetry (LSV) measurements. The formation process of these nanoparticles and the mechanism of the photocatalytic CO 2 RRs were proposed. In addition, this work provides an easy method for making ultrafine fragments (<10 nm) of a Co(II)-imidazole MOF or other MOFs, which could also be viewed as MOF nanoparticles or quantum dots stabilized by coordination of TEOA molecules.

A Valuable Biochar from Poplar Catkins with High Adsorption Capacity for Both Organic Pollutants and Inorganic Heavy Metal Ions

Liu Xia,Sun Ju,Duan Shengxia,Wang Yanan,Hayat Tasawar,Alsaedi Ahmed,Wang Chengming,Li Jiaxing

In this paper, biochar derived from poplar catkins was used as an economical and renewable adsorbent for adsorption organic and inorganic pollutants such as, dyes, organic compounds, and heavy metal ions from wastewater. Mesoporous activated carbonized poplar catkins (ACPCs) were produced from char as a by-product by carbonized poplar catkins (CPCs). With their high surface area, ACPCs exhibited the maximum adsorption capacities of 71.85 and 110.17 mg/g for the removal of inorganic U(VI) and Co(II). Compared other biochars adsorbents, ACPCs can also adsorb organic pollutants with the maximum adsorption capacities of 534, 154, 350, 148 and 384 mg/g for methylene blue (MB), methyl orange (MO), Congo red (CR), chloramphenicol (CAP) and naphthalene. The adsorption of organic pollutants was fitted with pseudo-first order, pseudo-second order, and intra-particle diffusion kinetic models figure out the kinetic parameters and adsorption mechanisms. Langmuir adsorption isotherm was found to be suitable for Co(II) and U(VI) adsorption and thermodynamic studies indicated adsorption processes to be endothermic and spontaneous. The adsorption process includes both outer-sphere surface complexes and hydrogen-bonding interactions. The results showed that biochar derived from poplar catkins was a potential material to remove pollutants in wastewater.

Rapid and selective spectrophotometric determination of peracetic acid in water via oxidative coloration of N,N-diethyl-p-phenylenediamine with the assistance of Co(II)

Siying Chen,Linfeng He,Jing Zou,Shiyi Yang,Lingxin Chen,Yingna Hou,Dongmei Xu,Zhongda Yan,Sheng Li,Jianying Wu

Peracetic acid (PAA) has garnered considerable interest due to its exceptional disinfection properties and strong oxidizing capabilities. However, the coexistent hydrogen peroxide (H 2 O 2 ) in the PAA solution, which has similar chemical characteristics with PAA, makes accurate measurement of PAA concentration challenging. In this study, a rapid, sensitive, and reliable spectrophotometric method for determining PAA was developed. The method involves the oxidation of N , N -diethyl- p -phenylenediamine (DPD) by Co(II)-catalyzed PAA, resulting in the formation of a stable pink DPD radical (DPD ●+ ). It is worth noting that Co(Ⅱ) is an excellent PAA catalyst but is inactive with H 2 O 2 . Consequently, there is minimal interference from the coexistent H 2 O 2 in the determination of PAA. The absorbance of DPD ●+ at 551 nm was well linear (R 2 > 0.999) with concentrations of PAA in the range of 0–80 μM under optimized reaction conditions, and the limit of detection was determined to be low as 0.175 μM. Furthermore, the proposed Co(II)-DPD spectrophotometric method demonstrates strong resistance to common natural water constituents (ferric ions, sulphate ions, nitrate ions, chloride ions, bicarbonate ions, and humic acid) and is suitable for the accurate determination of PAA in natural water sources like groundwater and surface water. Additionally, the proposed Co(II)-DPD spectrophotometric method was dependable for quantifying PAA concentrations and monitoring PAA changes in Co(II)/PAA, Cu(II)/PAA, Fe(II)/PAA, and hydroxylamine/Fe(II)/PAA processes. In conclusion, the proposed Co(II)-DPD spectrophotometric method can be utilized as an alternative method for the rapid and accurate determination of PAA in water.